CN106807361B - A kind of unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photochemical catalyst and preparation method - Google Patents
A kind of unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photochemical catalyst and preparation method Download PDFInfo
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- CN106807361B CN106807361B CN201710113548.0A CN201710113548A CN106807361B CN 106807361 B CN106807361 B CN 106807361B CN 201710113548 A CN201710113548 A CN 201710113548A CN 106807361 B CN106807361 B CN 106807361B
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 203
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 202
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims abstract description 166
- 239000002131 composite material Substances 0.000 title claims abstract description 105
- 239000003054 catalyst Substances 0.000 title claims abstract description 96
- MBIDWOISWGGCJD-UHFFFAOYSA-N [O].[Bi].[Bi] Chemical compound [O].[Bi].[Bi] MBIDWOISWGGCJD-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000008367 deionised water Substances 0.000 claims abstract description 28
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 28
- 238000013019 agitation Methods 0.000 claims abstract description 26
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000000151 deposition Methods 0.000 claims abstract description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 17
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 17
- 229910001868 water Inorganic materials 0.000 claims description 13
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 3
- 235000012054 meals Nutrition 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000008901 benefit Effects 0.000 claims description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000002242 deionisation method Methods 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 25
- 239000000126 substance Substances 0.000 abstract description 17
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract description 7
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 108
- 230000015556 catabolic process Effects 0.000 description 39
- 238000006731 degradation reaction Methods 0.000 description 39
- 229910000416 bismuth oxide Inorganic materials 0.000 description 30
- 238000007146 photocatalysis Methods 0.000 description 21
- 239000000243 solution Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 18
- 238000005406 washing Methods 0.000 description 16
- 239000011941 photocatalyst Substances 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- 229910002651 NO3 Inorganic materials 0.000 description 10
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 229910020350 Na2WO4 Inorganic materials 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 8
- 150000001621 bismuth Chemical class 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N CHCl3 Substances ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
- B01D2259/802—Visible light
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The embodiment of the present application shows the unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photochemical catalyst and preparation method: taking the presoma of bismuth element to be dissolved in deionized water, obtains bismuth solution, the presoma of tungstate radicle is taken to be dissolved in deionized water, obtains tungstate radicle solution；Bismuth solution and tungstate radicle solution are uniformly closed very much, isothermal reaction in an oven, obtains unformed bismuth tungstate powder；Reducing agent and unformed bismuth tungstate powder are dissolved in deionized water respectively, and carry out mixing magnetic agitation at room temperature, the unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photochemical catalyst is obtained by situ deposition method.In preparation method organic composite photochemical catalyst obtained provided by the present invention, Bi simple substance be supported in situ bismuth tungstate surface and and simple substance Bi oxide Bi2O3The light induced electron of unformed bismuth tungstate and the separation in hole pair can largely be accelerated by constituting hetero-junctions, and then the photocatalytic activity of ternary organic composite photochemical catalyst improves.
Description
Technical field
The present invention relates to photochemical catalyst preparation technical fields, more specifically, are related to a kind of unformed bismuth tungstate-of bismuth-
Bismuth oxide ternary organic composite photochemical catalyst and preparation method.
Background technique
With the progress of mankind's science and technology civilization, industry has obtained developing on a large scale, and automobile is also more more and more universal, largely
Discharged nitrous oxides enter in atmosphere.Nitrogen oxides as photochemical fog, acid rain, depletion of the ozone layer pollutant, nitrogen oxides
Have become countries in the world atmosphere pollution urgently to be resolved.It can be seen that the photocatalysis method of optical drive is as a kind of environmental-friendly green
Color technology has all shown good application prospect in environmental pollution purification and solar energy conversion aspect.It can be seen that optical drive
Photocatalysis method can make nitrogen oxides that oxidation reaction occur under photocatalysis, generate H2O, nitrate, nitrite etc. and
Reach innoxious, thus environment purification.
Studies have shown that bismuth series photocatalyst is a kind of good visible light catalyst.Kudo and Hijii is reported for the first time within 1999
Road bismuth tungstate has the activity of photochemical catalyzing.The research of Tang etc. confirms bismuth tungstate for CHCl3And CH3The mine of CHO
Change has photocatalytic activity.It is known that bismuth series photocatalyst since forbidden bandwidth is relatively narrow (1.76eV~3.1eV), causes photoproduction electric
Sub- hole is compound to being easy, and the photolytic activity of bismuth series photocatalyst is lower.In order to further increase the photolytic activity of bismuth series photocatalyst,
Many scholars are prepared using various distinct methods and the technologies such as doping and load with special appearance and the lesser tungsten of partial size
Sour bismuth photochemical catalyst.The prior art by improving preparation method, such as: precious metal doping load, building hetero-junctions technology, can be with
It effectively improves the visible absorption performance of bismuth based semiconductor material or inhibits the compound of light induced electron and hole, to further mention
Its high photocatalysis performance.
But the bismuth series photocatalyst that the preparation method of existing bismuth series photocatalyst prepares, optical response range is narrow,
Solar energy utilization ratio is low, and light induced electron and hole-recombination are serious, hinders the application of bismuth system photocatalysis technology.Therefore, seek one
Kind solar energy utilization ratio is high, and the preparation method of the stable bismuth series photocatalyst of photocatalysis performance is the task of top priority.
Summary of the invention
The object of the present invention is to provide a kind of unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photochemical catalysts
And preparation method, to solve bismuth class photochemical catalyst described in background technique, since optical response range is narrow, solar energy (visible light) benefit
It is low with rate, there is technical issues that and hinder photocatalysis technology the problems such as light induced electron and serious hole-recombination.
The embodiment of the invention provides a kind of unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photochemical catalysts
Preparation method, the preparation method comprises the following steps:
S101 takes the presoma of bismuth element to be dissolved in deionized water, obtains bismuth solution, and the presoma of tungstate radicle is taken to be dissolved in
Ionized water obtains tungstate radicle solution；
S102 uniformly closes the bismuth solution and the tungstate radicle solution very much, and isothermal reaction in an oven obtains unformed
Bismuth tungstate powder；
Reducing agent and the unformed bismuth tungstate powder are dissolved in deionized water by S103 respectively, and are mixed at room temperature
Magnetic agitation obtains the unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photochemical catalyst by situ deposition method.
It is selectable, the step of reducing agent and the unformed bismuth tungstate powder are dissolved in deionized water respectively packet
It includes:
Reducing agent and the unformed bismuth tungstate powder are taken, the reducing agent is described with the unformed bismuth tungstate powder
Molar ratio is 20%~120%；
It is described that reducing agent and the unformed bismuth tungstate powder are dissolved in deionized water respectively.
Selectable, the reducing agent is NaBH4。
It is selectable, the bismuth element presoma are as follows: bismuth nitrate.
It is selectable, the tungstate radicle presoma are as follows: sodium tungstate.
Selectable, in an oven in the step of isothermal reaction, the temperature in the baking oven is 100 DEG C, the reaction time
20h。
It is selectable, it is described that reducing agent and the unformed bismuth tungstate powder are dissolved in deionized water respectively, and in room temperature
Under in the step of carrying out mixing magnetic agitation, the magnetic agitation time is 30min.
The application second aspect shows a kind of unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photochemical catalyst.
From the above technical scheme, the embodiment of the present application shows a kind of unformed bismuth tungstate of bismuth-- bismuth oxide ternary
The preparation method of organic composite photochemical catalyst, the preparation method comprises the following steps: S101 takes the presoma of bismuth element to be dissolved in
In deionized water, bismuth solution is obtained, the presoma of tungstate radicle is taken to be dissolved in deionized water, obtains tungstate radicle solution；S102 will be described
Bismuth solution and the tungstate radicle solution uniformly close very much, and isothermal reaction in an oven obtains unformed bismuth tungstate powder；S103 will be gone back
Former agent and the unformed bismuth tungstate powder are dissolved in deionized water respectively, and carry out mixing magnetic agitation at room temperature, pass through original
Position sedimentation obtains the unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photochemical catalyst.Preparation provided by the present invention
In the unformed bismuth tungstate of method bismuth-obtained-bismuth oxide ternary organic composite photochemical catalyst, Bi simple substance is supported in situ
Bismuth tungstate surface and and simple substance Bi oxide bismuth oxide (Bi2O3) constitute hetero-junctions and can largely accelerate without fixed
The light induced electron of type bismuth tungstate and the separation in hole, and then visible light photocatalysis active is improved, meanwhile, it is negative relative to noble metal
For being loaded in bismuth tungstate surface and semimetal-organic composite photochemical catalyst for being formed, the unformed bismuth tungstate-bismuth oxide of bismuth-
Ternary organic composite photochemical catalyst is cheap, and preparation is simple, can be preferably applied for photocatalysis field.
Detailed description of the invention
To describe the technical solutions in the embodiments of the present invention more clearly, make required in being described below to embodiment
Attached drawing is briefly described, it should be apparent that, for those of ordinary skills, do not making the creative labor
Under the premise of, it can also be obtained according to these attached drawings other attached drawings.
Fig. 1 is the unformed bismuth tungstate of bismuth-provided in an embodiment of the present invention-bismuth oxide ternary organic composite photochemical catalyst
Preparation method flow chart；
Fig. 2 is the unformed bismuth tungstate-bismuth oxide of five kinds of different bismuths-prepared by the embodiment of the present invention 1,2,3,4,5
(XRD is the abbreviation of X-ray diffraction to the XRD diagram of ternary organic composite photochemical catalyst and the unformed bismuth tungstate of pure phase, i.e.,
X-ray diffraction)；
Fig. 3 is the unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photocatalysis prepared by the embodiment of the present invention 2
The SEM figure of agent (SEM is the abbreviation of scanning electron microscope, i.e. scanning electron microscope)；
Fig. 4 is the unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photocatalysis prepared by the embodiment of the present invention 3
The SEM figure of agent (SEM is the abbreviation of scanning electron microscope, i.e. scanning electron microscope)；
Fig. 5 is the unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photocatalysis prepared by the embodiment of the present invention 4
The SEM figure of agent (SEM is the abbreviation of scanning electron microscope, i.e. scanning electron microscope)；
Fig. 6 is TEM figure (the TEM transmission for the unformed bismuth tungstate of pure phase that the embodiment of the present invention 6 provides
The abbreviation of electron microscope, i.e. transmission electron microscope)；
Fig. 7 is the unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photocatalysis prepared by the embodiment of the present invention 3
The TEM figure of agent (TEM is the abbreviation of transmission electron microscope, i.e. transmission electron microscope)；
Fig. 8 is the unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photocatalysis prepared by the embodiment of the present invention 5
(TEM is the abbreviation of transmission electron microscope, i.e. transmission electron microscopy to the TEM figure of agent partial enlargement
Mirror)；
Fig. 9 is the unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photocatalysis prepared by the embodiment of the present invention 3
(HRTEM is the abbreviation of high resolution transmission electron microscope to the HRTEM figure of agent, i.e.,
High resolution transmission electron microscope)；
Figure 10 is five kinds of unformed bismuth tungstate-bismuth oxides three of different bismuths-prepared by the embodiment of the present invention 1,2,3,4,5
(UV-Vis DRS is UV-Visible to the UV-Vis DRS of first organic composite photochemical catalyst and the unformed bismuth tungstate of pure phase figure
Diffuse-reflection spectra, i.e. UV-vis DRS)；
Figure 11 is the unformed bismuth tungstate-bismuth oxide of five kinds of different bismuths-prepared by the embodiment of the present invention 1,2,3,4,5
The degradation efficiency comparison chart that ternary organic composite photochemical catalyst and the unformed bismuth tungstate of pure phase degrade to NO under visible light conditions；
Figure 12 is the unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photocatalysis prepared by the embodiment of the present invention 3
The O of agent2 -And OH-Figure is detected to the living radical of NO degradation under visible light conditions；
Figure 13 is the unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photocatalysis prepared by the embodiment of the present invention 3
Agent is degraded the test chart of NO stability under visible light conditions；
Figure 14 be the unformed bismuth tungstate of the bismuth-of the embodiment of the present invention 3-bismuth oxide ternary organic composite photochemical catalyst with
Time-resolved fluorescence figure (the The ns-level time-resolved that unformed bismuth tungstate is tested under visible light conditions
fluorescence decay spectrum)。
Marginal data:
The unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photochemical catalyst prepared by BWO-0.2 embodiment 1；
The unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photochemical catalyst prepared by BWO-0.5 embodiment 2；
The unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photochemical catalyst prepared by BWO-0.8 embodiment 3；
The unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photochemical catalyst prepared by BWO-1.0 embodiment 4；
The unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photochemical catalyst prepared by BWO-1.2 embodiment 5；
The unformed bismuth tungstate of BWO pure phase.
Specific embodiment
The embodiment of the invention provides a kind of unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photochemical catalysts
And preparation method, to solve described in background technique because unformed semiconductor material is without photocatalytic activity and because noble metal price is high
It is expensive and the problem of lead to photochemical catalyst higher cost.
The experimental principle of the application:
The visible light catalysis activity of unformed bismuth tungstate can be enhanced in the presence of Bi simple substance nano particle, and reason has several points,
One, the very strong surface plasma bulk effect of Bi simple substance nano particle can allow unformed bismuth tungstate to absorb more visible lights；Two,
Surface plasma can promote the electron excitation and transfer of Bi nano particle；Three, the fermi level of simple substance Bi is -0.17eV ratio
The conduction level 0.46eV of bismuth tungstate is more negative, is conducive to light induced electron and shifts from simple substance Bi to unformed bismuth tungstate.At the same time
Light induced electron is from Bi2O3Conduction band (0.33eV) shifted to the conduction band (0.46eV) of unformed bismuth tungstate, photohole is from unformed
The valence band (3.26eV) of bismuth tungstate is to Bi2O3Valence band (3.13eV) transfer, can effectively reduce photo-generate electron-hole in this way
Pair it is compound, have more light induced electrons can be used to restore O2Generate O2 -.And the superoxide radical with strong oxidizing property is
The important activity factor of photocatalytic degradation NO.
It is worth noting that: one word of molar ratio shown in the embodiment of the present application refers to NaBH4With the unformed wolframic acid
The molar ratio at bismuth meal end.
NaBH4Stablize under normal temperature and pressure.NaBH4Alkaline solution is in brown color.One of most common reducing agent.To in air
Aqueous vapor and oxygen it is more stable, operation processing be easy.
Attached drawing 1 is please referred to, the unformed bismuth tungstate of bismuth-provided by the embodiment of the present invention-bismuth oxide ternary is organic multiple
The preparation method of light combination catalyst the following steps are included:
S101 takes the presoma of bismuth element to be dissolved in deionized water, obtains bismuth solution, and the presoma of tungstate radicle is taken to be dissolved in
Ionized water obtains tungstate radicle solution；
S102 uniformly closes the bismuth solution and the tungstate radicle solution very much, and isothermal reaction in an oven obtains unformed
Bismuth tungstate powder；
Reducing agent and the unformed bismuth tungstate powder are dissolved in deionized water by S103 respectively, and are mixed at room temperature
Magnetic agitation obtains the unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photochemical catalyst by situ deposition method.
The application obtains the unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photocatalysis using in situ deposition method
Agent is directly by the Bi in bismuth tungstate3+It is reduced into simple substance Bi, without being to provide external source Bi, significantly more efficient can allow and restore
The bismuth simple substance come is adhering closely on unformed bismuth tungstate, so as to the transmission of light induced electron.
Experiment is it is found that the unformed bismuth tungstate of the bismuth-- bismuth oxide ternary prepared by above-mentioned preparation method by analysis
Organic composite photochemical catalyst, catalytic activity are higher than the catalytic activity of the unformed bismuth tungstate of pure phase, and relative to noble metal
For being supported on bismuth tungstate surface and semimetal-organic composite photochemical catalyst for being formed, the unformed oxidation of bismuth tungstate-three two of bismuth-
The cost of bismuth ternary organic composite photochemical catalyst in practical applications significantly reduces.
By urging the unformed bismuth tungstate of bismuth-prepared by the embodiment of the present invention-bismuth oxide ternary organic composite light
Agent is characterized, it can be seen that the unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photochemical catalyst has following spy
Property:
(1) bismuth tungstate unformed to bismuth-- bismuth oxide ternary organic composite photochemical catalyst carries out XRD analysis (such as Fig. 2
It is shown), it was demonstrated that Bi is existed simultaneously in the unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photochemical catalyst2O3Phase and Bi
Simple substance phase.
(2) bismuth tungstate unformed to bismuth-- bismuth oxide ternary organic composite photochemical catalyst carry out sem analysis (such as Fig. 3,
Shown in 4 and 5), it was demonstrated that the unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photocatalysis of preparation of the embodiment of the present invention
Agent is made of the microballoon and some nanometer sheets of some protrusions；Bismuth tungstate unformed to bismuth-- bismuth oxide ternary organic composite light
Catalyst carries out tem analysis (as shown in Fig. 6,7,8 and 9), it was demonstrated that the unformed bismuth tungstate-three of bismuth-of preparation of the embodiment of the present invention
It aoxidizes in two bismuth ternary organic composite photochemical catalysts, Bi Random Load is in unformed bismuth tungstate surface, while Bi2O3With it is unformed
It is closely contacted between bismuth tungstate, shows the unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite semiconductor light-catalyst
Successful building.
(4) bismuth tungstate unformed to bismuth-- bismuth oxide ternary organic composite photochemical catalyst carries out UV-Vis DRS analysis
(as shown in Figure 10) tests its optical response range, it was demonstrated that the introducing of Bi simple substance can reinforce the unformed bismuth tungstate of pure phase from it is ultraviolet-can
See-absorption of the infrared region to light, while can also be observed that the plasma absorption peak of Bi.
By degradation nitric oxide (NO) come to the unformed bismuth tungstate-bismuth oxide of bismuth-provided in an embodiment of the present invention
The catalytic performance of ternary organic composite photochemical catalyst is tested.Test process is as follows:
(1) the unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photochemical catalyst prepared by 0.2g embodiment is set
In in glass disk；
(2) four small fans are installed in reactor surrounding；
(3) under dark condition, when NO concentration reaches balance, with halogen tungsten light irradiation bismuth-unformed bismuth tungstate-of 150W
Bismuth oxide ternary organic composite photochemical catalyst 30min；After turn off the light, wait the concentration of NO to turn again to initial concentration and balance
Afterwards, it turns on light again, illumination 30min.
The condition of above-mentioned catalytic performance test process are as follows: relative humidity 60%；Oxygen content is 21%；The flow of NO air-flow
For 3.3L/min；The initial concentration of NO is 600 μ g/kg；The edge filter filtering ultraviolet light of 420nm is used before halogen tungsten light irradiation.
The unformed bismuth tungstate of bismuth-provided in an embodiment of the present invention-bismuth oxide ternary organic composite photochemical catalyst is to NO
The degradation of degradation is as follows:
(1) the unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photochemical catalyst is to the degradation rate of NO
12.5%-50.2% (as shown in figure 11) is higher than the unformed bismuth tungstate of pure phase to the degradation rate of NO, the calculation formula of degradation rate
For η (%)=(1-C/C0) × 100%, C0For initial NO concentration, C is the instantaneous concentration of NO after illumination 30min.
(2) superoxide radical (O2 -) it is that the unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photochemical catalyst exists
The main degradation free radical (as shown in figure 12) of degradation NO under visible light conditions.
(3) the unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photochemical catalyst can steadily degrade NO (such as
Shown in Figure 13).
(4) the unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photochemical catalyst can reuse, degradation effect
Fruit is almost the same (as shown in figures 11 and 13).
Figure 14 can be seen that the unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite light shown in the application implementation
The recombination time of the electron hole pair of catalyst is elongated, that is, enhances efficiently separating for electron hole pair.
In preparation method provided in an embodiment of the present invention, in order to make solution be uniformly dispersed, mixture solution need to be in ultrasonic wave
Middle dispersion 10min.When carrying out magnetic agitation, temperature is room temperature, is covered at beaker mouth with preservative film.
Several specific embodiments are enumerated with regard to preparation method disclosed in this invention below, described embodiment is only
A part of the embodiment in the present invention.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creation
All embodiments obtained shall fall within the protection scope of the present invention under the premise of the labour of property.
Embodiment 1:
By 1.390g Bi (NO3)3·5H2O and 0.473g Na2WO4·2H2O be scattered in respectively 40ml and 20ml go from
It in sub- water, mixes magnetic agitation 1h at room temperature later, is transferred to hydro-thermal 20h in 100 DEG C of baking oven, by washing drying
The unformed bismuth tungstate of pure phase is obtained afterwards；According to reducing agent NaBH4Respectively divide with the amount of the molar ratio 20% of unformed bismuth tungstate
It dissipates in the deionized water of 20ml, mixes magnetic agitation 30min at room temperature later, obtain bismuth-after washing is dry
Unformed bismuth tungstate-bismuth oxide ternary organic composite photochemical catalyst；It is subsequently installed in sample sack stand-by.
It is logical to the unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photochemical catalyst of preparation of the embodiment of the present invention
XRD, SEM, TEM, HRTEM, UV-Vis DRS is crossed to be characterized.
The unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photochemical catalyst of preparation of the embodiment of the present invention is to NO
It degrades, detailed process are as follows: in relative humidity 60%, oxygen content 21%, the flow of NO air-flow is 3.3L/min, NO's
Under conditions of initial concentration is 600 μ g/kg, the unformed bismuth tungstate of bismuth-- bismuth oxide ternary prepared by 0.2g embodiment is had
Machine composite photo-catalyst is placed in glass disk；Four small fans are installed in reactor surrounding；Under dark condition, 420nm is used
Edge filter filtering ultraviolet light, when NO concentration reaches balance, with halogen tungsten light irradiation bismuth-unformed bismuth tungstate-of 150W
Bismuth oxide ternary organic composite photochemical catalyst 30min；After turn off the light, wait the concentration of NO to turn again to initial concentration and balance
Afterwards, it turns on light again, illumination 30min.Unformed bismuth tungstate-the bismuth oxide three of bismuth-of preparation of the embodiment of the present invention is calculated
First organic composite photochemical catalyst is 12.5% to the degradation rate of NO, it is seen that Bi simple substance and Bi2O3It can be improved unformed bismuth tungstate pair
NO degradation rate.
Embodiment 2:
By 1.390g Bi (NO3)3·5H2O and 0.473g Na2WO4·2H2O be scattered in respectively 40ml and 20ml go from
It in sub- water, mixes magnetic agitation 1h at room temperature later, is transferred to hydro-thermal 20h in 100 DEG C of baking oven, by washing drying
The unformed bismuth tungstate of pure phase is obtained afterwards；According to reducing agent NaBH4Respectively divide with the amount of the molar ratio 50% of unformed bismuth tungstate
It dissipates in the deionized water of 20ml, mixes magnetic agitation 30min at room temperature later, obtain bismuth-after washing is dry
Unformed bismuth tungstate-bismuth oxide ternary organic composite photochemical catalyst；It is subsequently installed in sample sack stand-by.
To the unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photochemical catalyst of preparation of the embodiment of the present invention
Characterization and the composite photo-catalyst to the degradation test process of NO with embodiment 1.The bismuth-of preparation of the embodiment of the present invention is calculated
Unformed bismuth tungstate-bismuth oxide ternary organic composite photochemical catalyst is 39.7% to the degradation rate of NO.
Embodiment 3:
By 1.390g Bi (NO3)3·5H2O and 0.473g Na2WO4·2H2O be scattered in respectively 40ml and 20ml go from
It in sub- water, mixes magnetic agitation 1h at room temperature later, is transferred to hydro-thermal 20h in 100 DEG C of baking oven, by washing drying
The unformed bismuth tungstate of pure phase is obtained afterwards；According to reducing agent NaBH4Respectively divide with the amount of the molar ratio 80% of unformed bismuth tungstate
It dissipates in the deionized water of 20ml, mixes magnetic agitation 30min at room temperature later, obtain bismuth-after washing is dry
Unformed bismuth tungstate-bismuth oxide ternary organic composite photochemical catalyst；It is subsequently installed in sample sack stand-by.
Prepared by the unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photochemical catalyst table to the embodiment of the present invention
Sign and the composite photo-catalyst to the degradation test process of NO with embodiment 1.Bismuth-nothing of preparation of the embodiment of the present invention is calculated
Bismuth tungstate-bismuth oxide ternary organic composite photochemical catalyst of being formed is 40.8% to the degradation rate of NO.
Embodiment 4:
By 1.390g Bi (NO3)3·5H2O and 0.473g Na2WO4·2H2O be scattered in respectively 40ml and 20ml go from
It in sub- water, mixes magnetic agitation 1h at room temperature later, is transferred to hydro-thermal 20h in 100 DEG C of baking oven, by washing drying
The unformed bismuth tungstate of pure phase is obtained afterwards；According to reducing agent NaBH4Respectively divide with the amount of the molar ratio 100% of unformed bismuth tungstate
It dissipates in the deionized water of 20ml, mixes magnetic agitation 30min at room temperature later, obtain bismuth-after washing is dry
Unformed bismuth tungstate-bismuth oxide ternary organic composite photochemical catalyst；It is subsequently installed in sample sack stand-by.
To the unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photochemical catalyst of preparation of the embodiment of the present invention
Characterization and the composite photo-catalyst to the degradation test process of NO with embodiment 1.The bismuth-of preparation of the embodiment of the present invention is calculated
Unformed bismuth tungstate-bismuth oxide ternary organic composite photochemical catalyst is 50.2% to the degradation rate of NO.
Embodiment 5:
By 1.390g Bi (NO3)3·5H2O and 0.473g Na2WO4·2H2O be scattered in respectively 40ml and 20ml go from
It in sub- water, mixes magnetic agitation 1h at room temperature later, is transferred to hydro-thermal 20h in 100 DEG C of baking oven, by washing drying
The unformed bismuth tungstate of pure phase is obtained afterwards；According to reducing agent NaBH4Respectively divide with the amount of the molar ratio 120% of unformed bismuth tungstate
It dissipates in the deionized water of 20ml, mixes magnetic agitation 30min at room temperature later, obtain bismuth-after washing is dry
Unformed bismuth tungstate-bismuth oxide ternary organic composite photochemical catalyst；It is subsequently installed in sample sack stand-by.
Prepared by the unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photochemical catalyst table to the embodiment of the present invention
Sign and the composite photo-catalyst to the degradation test process of NO with embodiment 1.Bismuth-nothing of preparation of the embodiment of the present invention is calculated
Bismuth tungstate-bismuth oxide ternary organic composite photochemical catalyst of being formed is 30.7% to the degradation rate of NO.
Embodiment 6:
The unformed bismuth tungstate of pure phase provided in an embodiment of the present invention carries out degradation test process with embodiment 1 to NO.It calculates
Obtaining the unformed bismuth tungstate of pure phase is 10.6% to the degradation rate of NO.
Embodiment 7:
By 1.390g Bi (NO3)3·5H2O and 0.473g Na2WO4·2H2O be scattered in respectively 40ml and 20ml go from
It in sub- water, mixes magnetic agitation 1h at room temperature later, is transferred to hydro-thermal 20h in 120 DEG C of baking oven, by washing drying
After obtain pure phase bismuth tungstate；Identify that this pure phase bismuth tungstate is crystallized by XRD.
Due to crystallized, do not meet proposed by the invention will solve the pure phase bismuth tungstate that the embodiment of the present invention is prepared
Unformed semiconductor premise of modification without photocatalytic activity, thus it is successive modified experiment carry out again it is meaningless.
Embodiment 8:
By 1.390g Bi (NO3)3·5H2O and 0.473g Na2WO4·2H2O be scattered in respectively 40ml and 20ml go from
It in sub- water, mixes magnetic agitation 1h at room temperature later, is transferred to hydro-thermal 20h in 140 DEG C of baking oven, by washing drying
After obtain pure phase bismuth tungstate；Identify that this pure phase bismuth tungstate is crystallized by XRD.
Embodiment 9:
By 1.390g Bi (NO3)3·5H2O and 0.473g Na2WO4·2H2O be scattered in respectively 40ml and 20ml go from
It in sub- water, mixes magnetic agitation 1h at room temperature later, is transferred to hydro-thermal 20h in 100 DEG C of baking oven, by washing drying
The unformed bismuth tungstate of pure phase is obtained afterwards；According to reducing agent NaBH4Respectively divide with the amount of the molar ratio 100% of unformed bismuth tungstate
It dissipates in the deionized water of 20ml, mixes magnetic agitation 1h at room temperature later, it is fixed to obtain bismuth-nothing after washing is dry
Type bismuth tungstate-bismuth oxide ternary organic composite photochemical catalyst；It is subsequently installed in sample sack stand-by.
To the unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photochemical catalyst of preparation of the embodiment of the present invention
Characterization and the composite photo-catalyst to the degradation test process of NO with embodiment 1.The bismuth-of preparation of the embodiment of the present invention is calculated
Unformed bismuth tungstate-bismuth oxide ternary organic composite photochemical catalyst is 38.4% to the degradation rate of NO.
Embodiment 10:
By 1.390g Bi (NO3)3·5H2O and 0.473g Na2WO4·2H2O be scattered in respectively 40ml and 20ml go from
It in sub- water, mixes magnetic agitation 1h at room temperature later, is transferred to hydro-thermal 20h in 100 DEG C of baking oven, by washing drying
The unformed bismuth tungstate of pure phase is obtained afterwards；According to reducing agent NaBH4Respectively divide with the amount of the molar ratio 100% of unformed bismuth tungstate
It dissipates in the deionized water of 20ml, mixes magnetic agitation 10min at room temperature later, obtain bismuth-after washing is dry
Unformed bismuth tungstate-bismuth oxide ternary organic composite photochemical catalyst；It is subsequently installed in sample sack stand-by.
The difference of embodiment 4, embodiment 9 and embodiment 10 is only that, NaBH4Under magnetic stirring with unformed bismuth tungstate
Reaction time.Embodiment 4NaBH4Mixing time with unformed bismuth tungstate is 30min, the organic composite photochemical catalyst of synthesis
Degradation rate to NO is 50.2%,.Embodiment 9NaBH4Mixing time with unformed bismuth tungstate is 1h, the organic composite of synthesis
Photochemical catalyst is 38.4% to the degradation rate of NO；Embodiment 10, NaBH4Mixing time with unformed bismuth tungstate is 10min, is closed
At organic composite photochemical catalyst be 43.5% to the degradation rate of NO.
It can be seen that in NaBH4Mixing time with unformed bismuth tungstate is NaBH in the time range of 10min -30min4With
The mixing time of unformed bismuth tungstate is longer, and the organic composite photochemical catalyst prepared is higher to the degradation rate of NO, if but
NaBH4Mixing time with unformed bismuth tungstate is more than 30min, continues to extend mixing time, the organic composite light prepared
Catalyst reduces the degradation rate of NO.
Known extension NaBH4With the mixing time of unformed bismuth tungstate, the bismuth simple substance being reduced is oxidized again, and then is made
The organic composite photochemical catalyst that must be prepared reduces the degradation rate of NO.
To the unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photochemical catalyst of preparation of the embodiment of the present invention
Characterization and the composite photo-catalyst to the degradation test process of NO with embodiment 1.The bismuth-of preparation of the embodiment of the present invention is calculated
Unformed bismuth tungstate-bismuth oxide ternary organic composite photochemical catalyst is 43.5% to the degradation rate of NO.
The following table 1 is the degradation rate that each photochemical catalyst degrades to NO in above-described embodiment 1-10.
As it can be seen from table 1 by Bi simple substance and Bi2O3Deposition modifies the unformed bismuth tungstate-of bismuth-of unformed bismuth tungstate
Bismuth oxide ternary organic composite photochemical catalyst to the degradation of NO relative to the unformed bismuth tungstate of pure phase for the degradation of NO,
The former degradation rate significantly improves, and degradation effect is obvious.And Bi replaces noble metal compound with unformed bismuth tungstate and prepares multiple
Light combination catalyst can reduce the cost of photochemical catalyst in practical applications.
From the above technical scheme, the embodiment of the present application shows a kind of unformed bismuth tungstate of bismuth-- bismuth oxide ternary
The preparation method of organic composite photochemical catalyst, the preparation method comprises the following steps: S101 takes the presoma of bismuth element to be dissolved in
In deionized water, bismuth solution is obtained, the presoma of tungstate radicle is taken to be dissolved in deionized water, obtains tungstate radicle solution；S102 will be described
Bismuth solution and the tungstate radicle solution uniformly close very much, and isothermal reaction in an oven obtains unformed bismuth tungstate powder；S103 will be gone back
Former agent and the unformed bismuth tungstate powder are dissolved in deionized water respectively, and carry out mixing magnetic agitation at room temperature, pass through original
Position sedimentation obtains the unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photochemical catalyst.Preparation provided by the present invention
In the unformed bismuth tungstate of method bismuth-obtained-bismuth oxide ternary organic composite photochemical catalyst, Bi simple substance is supported in situ
Bismuth tungstate surface and and simple substance Bi oxide Bi2O3The light of unformed bismuth tungstate can largely be accelerated by constituting hetero-junctions
The separation of raw electronics and hole, and then visible light photocatalysis active is improved, meanwhile, relative to noble-metal-supported in bismuth tungstate table
Face and for semimetal-organic composite photochemical catalyst for being formed, the unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite
Photochemical catalyst is cheap, and preparation is simple, can be preferably applied for photocatalysis field.
It should be noted that the unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite provided in an embodiment of the present invention
Photochemical catalyst to sulfide, volatile organic compounds, non-NO other air pollutants such as oxynitrides catalytic mechanism
It is identical as the catalytic mechanism to NO therefore representative by the degradation test to NO in the embodiment of the present invention.
It is obvious to those skilled in the art although describing the present invention in a manner of specific embodiment
, in the case where not departing from the spirit and scope of the present invention defined by the appended claims, can to the present invention into
Row variations and modifications, these change and modification are also included in the scope of the present invention.
Claims (6)
1. a kind of unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photochemical catalyst preparation method, feature exist
In the preparation method comprises the following steps:
S101 takes the presoma of bismuth element to be dissolved in deionized water, obtains bismuth solution, and the presoma of tungstate radicle is taken to be dissolved in deionization
Water obtains tungstate radicle solution；
S102 uniformly closes the bismuth solution and the tungstate radicle solution very much, and isothermal reaction in an oven obtains unformed wolframic acid
Bismuth meal end；
Reducing agent and the unformed bismuth tungstate powder are dissolved in deionized water by S103 respectively, and carry out mixing magnetic force at room temperature
Stirring, obtains the unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photochemical catalyst by situ deposition method；
Described the step of reducing agent is dissolved in deionized water with the unformed bismuth tungstate powder respectively includes:
Reducing agent and the unformed bismuth tungstate powder are taken, the molar ratio of the reducing agent and the unformed bismuth tungstate powder is
20%~120%；
It is described that reducing agent and the unformed bismuth tungstate powder are dissolved in deionized water respectively；
The reducing agent is NaBH4。
2. preparation method according to claim 1, which is characterized in that the bismuth element presoma are as follows: bismuth nitrate.
3. preparation method according to claim 1, which is characterized in that the tungstate radicle presoma are as follows: sodium tungstate.
4. preparation method according to claim 1, which is characterized in that in an oven in the step of isothermal reaction, the baking
Temperature in case is 100 DEG C, reaction time 20h.
5. preparation method according to claim 1, which is characterized in that described by reducing agent and the unformed wolframic acid bismuth meal
End is dissolved in deionized water respectively, and in the step of carrying out mixing magnetic agitation at room temperature, the magnetic agitation time is
30min。
6. a kind of unformed bismuth tungstate of bismuth-- bismuth oxide ternary organic composite photochemical catalyst, which is characterized in that by above-mentioned power
Benefit requires preparation method described in any one of 1-5 to be prepared.
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| CN109482172B (en) * | 2018-12-29 | 2021-03-09 | 陕西师范大学 | Degraded NOxBi/CeO of (A)2Composite photocatalyst and preparation method thereof |
| CN109482171B (en) * | 2018-12-29 | 2021-03-09 | 陕西师范大学 | Bi/beta-Bi2O3Nanometer flower ball shaped photocatalyst and preparation method thereof |
| CN109692698B (en) * | 2018-12-29 | 2021-03-09 | 陕西师范大学 | Bi/Ti for catalytic reduction of NOx3C2Nano-sheet photocatalyst and preparation method thereof |
| CN110624535A (en) * | 2019-09-17 | 2019-12-31 | 江苏大学 | Black bismuth tungstate photocatalyst as well as preparation method and application thereof |
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| CN112871183B (en) * | 2021-02-20 | 2023-07-25 | 徐州工程学院 | Preparation method of bismuth/bismuth tungstate/ferroferric oxide composite photocatalyst |
| CN114011403B (en) * | 2021-12-16 | 2022-07-12 | 广东工业大学 | Preparation method and application of amorphous bismuth tungstate photocatalytic material |
| CN114289013B (en) * | 2021-12-24 | 2024-07-19 | 广州工业智能研究院 | Bismuth-amorphous bismuth tungstate photocatalyst, and preparation method and application thereof |
| CN114247452A (en) * | 2022-01-10 | 2022-03-29 | 山东农业大学 | Bismuth-bismuth sulfide-bismuth tungstate composite photocatalyst and preparation method and application thereof |
| CN114392750A (en) * | 2022-02-17 | 2022-04-26 | 齐鲁工业大学 | Bismuth/bismuth ferrite visible-light-induced photocatalyst material and preparation method and application thereof |
| CN115254187B (en) * | 2022-08-03 | 2023-06-30 | 江苏理工学院 | Preparation method and application of mesoporous amorphous bismuth tungstate photocatalytic material |
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